Integral mask for color film



` QR. M. EVANS i v 2,203,653

INTEGRAL kMASK FOR coLon FILM Filed Aprile?. 1957 'wk erm" m Z8 nulummmnm Gow @ffy v f u f 10 f f lor Pos/hoe. /mages QGo/d Mggqffog 'and Color Psdluelma es Ralph.MEVcmSj @.MMMZ

ATTORNEYS Patented June 4, 1940 l PATENT ori-ICE `throat-53 INTEGRAL MASK Foa ooLoR FILM Ralph M. Evans, Rochester, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y., a `corporation of New Jersey Application April 27, 193'7,`Serial No. 139,252

3 Claims.

`This invention relates to color, correction Vin printing color transparencies and particularly to an integral mask for securingcolor correction in printing high-contrast color transparencies.

In photo-mechanical process work where a colored original is to be copied, it is necessary to make some correction for the deficiencies of the positive inks or pigments used to print the iinal picture. This correction may be done by hand retouching, but masking methods have been devised in which positives of vlow contrast are used to mask the. color-separation negatives or certain of Vthe color-separation negatives in `order to overcome these deficiencies in the ink. For example, masks are used for the green and blue filterseparation negatives, respectively, in exposing the magenta and yellow printing positives. This procedure lowers the density of' the magenta` and yellow positives in those portions of the picture where blue-green is printed and hence lowers the` Vcontrast of the magentaand yellow images inthe scale of greys. When compensation `for this iowering of contrast is made, as by increasing the contrasts of the green and blue iter negatives, the scale of greys is correctly rendered and the saturations ofthe magenta, yellows and reds is increased. At the same time the amountof mag- `enta printed evergreen and of yellow printed over blue remains less than without color correction.,

thus compensating forthe greenor blue light absorption of the blue-green ink or pigment.

Thismethod of color correction is applicable only to color-separation `images and cannot be employed in printing color transparencies, suchv as multi-colored images contained in gelatin lay- `ers on a single support. In lms or plates of this type a natural-color image is` contained on a single film and may be projected or viewed without recourse to filters, or mechanical or optical colorforming arrangements.

trast of the color process deepens and sharpens these absorption bands and` so tends togive a color `which may be made `equal to, or `higher than, the saturation of the original. i

When an attempt istmade to duplicate such a` color photograph by means of `the same process` In general, in color i processes of `this type it is desirable to have a ori any other process which has a high contrast, theiinished duplicate has too` great -a contrast, or gamma, since the gammas of the two images multiply on printing. In printing color photographs of this type, the contrast may be lowered by inserting a negative image of the black-and- White values of the original over thecolor photograph during pprinting. However, this method introduces the necessity of securing exact registry of the color photograph and of the negative mask, which is accompanied by time-consuming diliiculties. Itis also necessary to resort to an extra printing step in order toobtain this negative Imasking image.

It is, therefore, an object of the present'invention to provide a means for'masking in order to secure color correction in printing naturalcolor transparencies. A further object yis to provide a masking means which eliminates the necessity of registration of the original and masking images duringprinting. Other objects will appear from the following description of my invention.

, These objects are accomplished by forming a mask representing the black-and-white values of the original subject,lthe mask being'integral with the original iilm or plate and in the'same photographic layer or layers. Methods and meansfor accomplishing these results comprise the subject of the present invention.

In the accompanying drawing Fig. 1 is a flowdiagram representing enlarged sectional views of a film showing one method of forming a masked image according to my invention.

Fig. 2 is a flow-diagram representing enlarged sectional views of a film showing the stages in another method of :forming a masked image according to my invention.

The general method of procedure according to my` invention consists in forming the masking `image `as part of the original process of making the color original. `No registry problems are,

therefore, involved.

According to my preferred method 'of procedure la lrn t is used having three-superposed diiierentially sensitized photographic layers on `one side of a support. A film of this type is described in Patent No. 2,113,329, granted April 5, 1938, to L. D.Mannes` and L. Godowsky, Jr. This lm is designed for exposure in acamera and the `formation of images by a coupling of the oxidation product of the developer with a coupling compound.A The` coupling compound may be contained in the developer or may be present origj inally as a substantially colorless substance in the photographic layers. i

. After exposure, the film is developedin an ory dinarydeveloper, such as an elon-hydroquinone developer, which forms metallic silver images at the exposed portions of the film. A film of this type is shown in Fig. 1 of the drawing which represents a'lm after exposure to a step wedge, .that is, a gray scale. As shown in Fig. 1, I 0 isa transparent support of any suitable material, such as glass ora cellulose ester having superposed thereon layers II, I2 and I3 sensitive, respectively, to red, green and blue light. A yellow filter dye may be contained in the layer I3 or` v between the layers I2`and I3 to, prevent the ac- .baths used in subsequent steps of the color-forming process.

A substance of this type is metallic gold and as shown in the second sqtage of Fig. 1 the silver images have been transformed to vmetallic gold "images I'I, I8 andi 1I9. The gold images are representedas being of more grainy structure than the silver images. This is merely for the purpose of distinguishing the illustrations and is not necessarily true in practice.

During this procedure, the sensitive silver salt l in the unexposed portions of the film has not been aiiected and it may, therefore, be exposed andi redeveloped to formcolored images. The film is re-exposed and subjected to a series of colorforming steps, for example, as described in Patent- No. 2,113,329 and colored images are thereby formed in\ the unexposed portions of each of the layers. As shown in the third stage of Fig. 1, by

thissprocedure a blue-green image is formed in layer II, a magenta. image 2I is formedl in layerv I2 and a yellow image 22 is formed .in vlayer I3. l

When this iilm is used to print onto a similar film in which colored images are to be formed,A the masking images I'I, I8, `I9 reduce the contrast of the colored images 20, 2| and 22 without affecting their color saturation andI thereby enable the i Amaking of a print having colored images of' correct contrast.l

. Itis also possible, according to my invention.I to

control several variables useful in the reproduction of colored images. In additionto the control-of contrast, as described above, it is also possible to control color balanceand overall density of the print.

The color balance of a color process may vary in numerous ways. Considering three-color subvtractive processes, the effective speeds of the process to the three primary colors may be different, or the light source used to expose the picture may have a different spectral limage distribution than that for which the film was designed, or the picture for some reason may have been exposed through a flter which has altered the spectral distribution of the light source. All.;`

these have the effectof shifting the color response curvesiparallel to each other. Forthese defects,

. n'o treatmentL of the vmask is effective but its action under all conditions permits of correction i inthe printing process by `a change in the color" sensitivity balance of the color process used for reproduction to the extent that this' is possible without the mask. The color photograph may also have incorrect color balance because the effective gammas of the three color-curves are different. Inthis case the color mask permits of .modification in the relative color gammas during the duplicating process by modification of the spectral energy distribution of the light used in the final printing operation without interfering with 'the colors so obtained.

Another type of lack of color balance arises' from the fact that the dyes' used in the original colored image do not-all have equal color purities.

Assume for illustration that thefyellow record has no absorption in its maximum transmission region, that the magenta record has some absorption in its transmission regions b ut chiefiy in its blue transmission band, and that the blue-green record has a considerable absorption in the blue f and green regions. This is typical of most color processes. The action of a yellow` filter in .mak-

ing a separate mask, would thenbe as follows: The mask would receive an `exposure which was not affected `by the yellow image but decreased slowly by increasing magenta 'image and decreased more rapidly by increasing blue-green image'.l` The use of this mask/in registry with the image would accordingly tend to give an uniform admixture vof black with all colors of the record. By extending this method the mask may be made to overcompensate for the lack of purityof thc dyes in the picture being copied in such a way'that partial compensation may be obtained for the process.

According to mymethod vof procedure some -impurity of the dyes usedin the reproduction correctiton for lack of color balance and deficien ,cies in the transmission of the positive dyes used may be obtained simultaneously with reduction of contrast during the printing'op'eration.

This is illustrated by the following method.

As shown in Fig. 2 metallic silver images I4, I5 y' and I6 are formed in layers II, I2 and I3 in the same manner as in the method described above. The film isthen treated in a neutral potassium permanganate bleach bath which may be controlled with respect to diffusion into the layers. This bleach bath reduces the density of the silver images and may be allowed to entirely destroy the4 silver image in the upper layer or layers. After this bleaching operation, as shownin the next stage of Fig. 2 the'lm contains a'silverfimage 23 of slightly reducedl denvsityin the lowest layer II,

'a silver image 24v in 4layer I2 in which the ypermanganate bleach has proceededt'o such an extent that the image is reduced in density asshown at 25. The silver image in the layer I3 has Ythen been substantially entirely dissolved vas shown at 26. The film is then treated in a sulte bath to remove oxidation products of the permanganate,

and the metallic silver images converted to metallic gold as in the previous method of procedure."

The extent to which the silver images are' converted to metallic gold imagesior example, by

varying the time of treatment, concentration, etc., of the gold toning bath may also be .controlled so that the gamma of/the gold masking images Ymay be controlled at-this step. n trol of the amount of contrast reduction obtained. As shown in the third stage of Fig. f2, the filml stage. f In the gold toning operation themetallic silver ..70 then contains metallic gold image 21 in layer II and metallic gold image` 2,3' in layer I 2. )The layer I3 contains no visible metallic image at-this of the image is converted to the silver saltcorresponding to the original gold salt or to the most insoluble silver compound that can be formed from the ions present.` This silver salt must `be removed along with any remaining unoxidized metallic silver. This `may be done in various Ways. If the gold saltis gold thiocyanate,silver thiocyanate is formed and this `may be quantitatively re-convertedto` metallic salt by re-mmersion for a short time in a metol-hydroquinone developer, all the silver is then removed by a permanganat sulfuric acid bleach. If the gold salt is gold sulfate the silver is converted to silver sulfate which is partially soluble in water or acid but is also completely removed by a subsequent permanganate or acid bath. If the goldsalt is gold chloride a differentialv xing bath may be used which removes the silver chloride but not the` silver bromide, which is` necessary for subsequent formation of the colored image. i

The film after formation of the gold masking i images 2l and 28 is then subjected to the processing procedure described in Patent No. 2,113,329

zand `blue-green image 2U, magenta image 2l and `yellow image `22 are formed in the layers ll,` l2

and i3, respectively. This isA shown in the last stage of Fig. 2 of the accompanying drawing.

`,Since the blue-green image requiresthe greatest amount of correction and the magenta image requires a less amount of correction, the gold images El and EB are designed in this modicationi of my `invention to reduce the contrast of the blue-green and magenta images without affecting that of the yellow image, so that a correction for color balance is thereby obtained.

The following specific example illustrates the i method of forming masking images as` illustrated `in Fig, 2 of the drawing.

The three-layer film after exposure is developed in a developer of the following composition:

Monomethyl paraaminophenol i sulfate grams-; 4,.) Hydroq'iinone Q do l0 Sodium sulte do 75 Sodium carbonatem do 30 Potassium bron1icle f do 4.5 Potassium thiocyanatedo l` 50 Water to liter-- l VLin order to .reduce the density of the `metallic silver image in the toplayer and part of the middle layer and any `developerfcig which the iilm may contain, the film is treated n a permanganate bleach bath `of the following com- Potassium pernlanganate` grams 2.5 Sodium sulfate do 140` Sodium chloride do\. 5 Acetic acid c. c.- 2 Water to; liter 1 After a few minutes the silver image in the top layer is completely removed while the two `lower images are only slightly affected. The time of treatment in the permanganate bath maybe controlled to determine the relative amounts of silver image left in the three layers, although the` top image is always removed to a greater extent than the lower ones.

In order to remove the `oxidation products of` the permanganate resulting vfrom treatment in the toning bleach bath thefilm is then treated fora few minutes in a bisulte clearing bath consisting of 15 grams of `bisullite per liter of water.

' of the .masking image.

The nlm i then treated in a gold toning bath of the following composition:

Gold chloride grams per liter 2 to 2.5 Sodium acetatesuflicient to vbuffer to apH of 4.5

The lm after treatment for a few minutes in the gold toning bath or for a sufficient length of time to form a gold image of the desired density is subjected to an ammonia. differential fixing bath comprising a saturated aqueous solution of silver bromide containing 32 grams per liter of ammonium hydroxide.

"The formationof the masking image is thereby completed and the filmI is next subjected to an acid permanganate bleach bath of the following composition:

Potassium permanganate (4% solution).

, grains..V l sulfuric acid (20% solution) do 1 Water do- 20 |lihis removes anyv residual metallic silver and prepares the film for` re-exposure and de-y velopment to form colored images as described in` Patent No. 2,113,329.

The gold mask formed according to :my invention is almost a neutral gray, having a slight bluish color. It is not necessary for the mask to be a neutral gray, however, as any spectral color may be used in the mask, the color being chosen with regard to such correction of the color balance and other factors as may be necessary.

Other methods of forming masks may be resorted to according to my invention. Instead of forming a mask of gold or other inert metallic substanceit is also `possible to use a dye whose silver salt is insoluble and which is suliiciently stable to withstand the action of the oxidizing i and reducing baths ofthe color-forming 'process to which the hlm is` subjected after formation Such dye may be `applied after the negative development in conjunction with an oxidizing bath which is capable of converting metallic silver to the dye salt. It is also possible to carry out the original negative development in a developer consisting essentiallyof a developing agent,.coupling agent, sulte and alkali so that there` is formed, simultaneously with `the formation ofthe negative silver image, aninsolubie dye image of the required color which will remain after the removal of the silver image. l

it is to be understood that numerous modifications and changes may be made' in the specific features of my invention and that my invention is to be taken as limited only by the scope of 'the appended claims.

What Iclaim is:

l. A photographic element for printing a colored image `having substantially the same color values as the eriginal subject, comprising three superposed gelatin layers containing positive substantially pure dye` images which tolgether form a natural-color image of the subject, and at least one metallic gold negative image of the subject, having sufficient density to serve as a correcting mask on printing and `being inert to silver solvents, in the same' photographic layers.

2. The method of making a colored photographic printing element, which comprises exposing a multi-layer, dilerentially-sensitized photographic element to a colored object, formi ing at least one metallic gold, negative image of the object in the element, said image being a ferentially-sensitiZed to recordA the primary negative image representing the color which the layer in which is it located records, and having suicient density to serve as a correcting mask on printing, -and thenforming a positive, substantially cure dye image of the object inthe same velement by a treatment: involving the use offsi'lver solvents. y

3. 'Ihe method of making a colored photographic printing element, which comprises exposing a lm having three superposed layers difaeoaess col-ors, to 'a natural-coior object, treating the film to form at least one metallic gold, negative image ofthe object in the layers, said negative image being a negative image representing the color which the layer in'which it is located records, and then forming 'a positive, naturalcolor image of the object in the layers by a. treatment yinvolving the use of a. permanganate solution.

RALPH M" EVANS. 10 

